Creating novel structures by self-assembly processes and fixing the resultant assemblies are both critical to the design and fabrication of functional materials through bottom-up approaches. We demonstrate magnetically induced self-assembly of 2D photonic labyrinth structures and their solidification through a sol-gel method. The photonic labyrinth structures can be patterned into more regular arrangements using nonmagnetic substrates. This work may provide a platform for fabricating novel materials and devices with complex morphologies and spatial configurations.